Acid disazo dyestuffs



Patented July 1, 1952 p AommsAzo DYESTUFFS Franz FrisclilhBasehSwitzerland; assignor to'g SandomLimitei; Basel, Switzerland, a Swissminimise; Angli an-m;.Febmaifiama S cl, rial,- N -oi -76-, 418. InSwltzerlandcEebruary 17,

i 4 omits; 01. 260191) fto blackshades and ma process napasentiaveneeerelates to" new; valuable Thedyestufisfalling m the scope orthe abovegeneral formula dye' wool and natural sill;

from a neutral or a weakjacid bath into violet; blue to black shadespossessing good fastness pro'pertiesjto'- 'alkaline1and acid milling;sulfur:

" bleachingand to light; I

Nlaralkyl SO -ary l atoms, the aryl radical being, if desired;substituted by 'alkyl or cycloalkyl radicals, and Y stands for hydrogenalkyl i gen, in an acid medium" with2-amino-8-hydroxynaphthalenee6rsulfonic' acid or their N-alkyl-l andN-aryl derivative's.

The disazo dyestuffs thus obtainedworrespond,

therefore,- to the gen'eral formula:

wherein X and Y have the above meanings and R stands for hydrogen, alkyland aryl,

H Hi

The. e ff r d', e i ne prod diazotizingian' amine of the iormula nets intl 'emfesent processmaybe p'reparediby;

wherein X and Y stand for the substituents cited above, and coupling thediazo compound thus ob tained" with1-amino-3-aryl-sulfoylaminobenzenei-fi-sulionic acid, whereupon theproduct thus obtained will be treated with alkylating agents,

order to"iiitroduce an alkyl group into the 'arylsulfoylamino radical ofthe coupling component citedaliove. The monoazo dyestuffs thus obtainedwill then be used as starting material for the coupling with theZ-amino-B-hydroxynaphthalene-S-sulfonic acidor its N-alkyl or N- arylderivatives giving dyestuffs dyeing animal fibreslinto violet, blue toblack shades.

As compared to the known dyestuffs which can be prepared"according toGerman Patent Specificat1on 695,4qi;-t1ie dyestuffs prepared accordingto the present process possess an improved fastness tdmilIing aa betteraffinity to the fibres, when applied" from a neutral bath, and in somecases a better stability of the shade in artificial light.

The following examples, without being limitative, illustrate the=presentinvention, the parts Example '1 22:2 parts ofz-aminol-chlorodiphenylether are diaz'otized' in the usual manner and coupled in the presenceof sodium carbonate with a solution of 34.2 parts of1-ai'nino-3-(4'-methyl) phenylsulfoylaminobenzene 6 --sulfonic acid.After the coupling has finished, the aminoazo dyestufi' is separated,dissolved in water with addition of--fparts of caustic soda lye 30% andtreated with 20 parts of dimethyl sulfate until the dyestuftmethylatedin the substituted amino gfoupmprecipitates. It is :then suspended inwater and diazotized at about 5 C. by means of 7 parts of sodium nitriteand 35 parts of concentrated hydrochloric acid. The diazoazo compoundwhich precipitates is filtered and coupled wool and silk from a neutralor a slightly acid dye-bath into blue shades of good fastness toalkaline and acid milling and to light. The dyestufi corresponds to theformula 7 Examplez 16.3 parts of p-tert.-amylaniline are diazotized andthe diazo solution combined with a s0- dium carbonate alkaline solutionof 34.2 parts of 1-amino-3- (4'-methyl)phenylsulfoylaminobenzene-S-sulfonic acid. After the coupling isfinished, the aminoazo 'dyestufi is separated and methylated withdimethylsulphate in the. manner described in Example 1. It is thenfurther di- I 4 by filtration. In dry state it is a blue powder, solublein water with a blue coloration. It dyes wool and natural silk from aneutral or a slightly acid dye-bath into blue shades of good fastnessto. alkaline and. acid milling and light.

. 18.5 parts of p-aminodiphenyl ether are diazotized and the diazosolution combined with a sodium carbonate solution of 32.8 parts ofl-amino- 3 phenylsulfoylaminobenzene 6 sulfonic acid. After completionof the coupling the aminoazo dyestufi is isolated by filtration,dissolved in water under addition of 80 parts of caustic soda lye 30%and treated at room temperature with 22 parts of diethyl sulfate, untilthe dyestufi ethylated only in the phenylsulfoylamino groupprecipltates; It is then filtered, suspended in water and diazotized bymeans of 7 parts of sodium nitrite and 35 parts of concentratedhydrochloric acid. The diazo compoundthus obtained is file tered andcoupled in an acid medium with 32.5 v

parts Of 2-o tolylamino-8-hydroxynaphthalene f "tained is thensaltedout, filtered and driedn It. is soluble in' waterwith a blue colorationand dyes wool and silk from a neutral or slightly. acid dyebath intofull black shades of good fastness to sulfur bleaching and milling andvery good *fastness to light.

The following table shows the manufacture of further disazo dyestufisaccording to the present invention.

Coupling Shade on dyestufi Component W00 1 A -2-amino-8-hyblue.

0.0]! 7 $03K droxynaph- I tllfilneinei 1 liT-CH:

" so.-C -om 2 id. reddish 80 t rom N--N=N NH:

l I OH:

3 Cl HOlH id. eenlsh 1:11. I blue. NON=N NH: lo OH 4. BOaH id. reddishblue. OHzQ-N=N NH:

01 CHI Aminoazo dyestufi 83 21252? shggglon 21 5/0111z-p-wlyleminogreenish 8-hy d r ox yblack.

CHaN-S0z -CH:

22 SOxH id. black.

23 S O :H 2 (trimethylreddish phenyl)-amlblack.

The dyestufi corresponding to item 7 0f the and an alkyl group with 5carbon atoms, Y stands foregoing table corresponds to the formula: for asubstituent selected from the group con- 01 303E NH sisting of hydrogen,chlorine and lower alkyl, R 1 25 stands for a substituent selected fromthe class ON=NN=N consisting of hydrogen, lower alkyl and aryl and I IR1 stands for a member selected from the group 7 o N-OH; H0 consistingof hydrogen, lower alkyl and cyclohexyl. S m-0153 $0311 2; The aciddisazo dyestuff of the formula Cfiz /CH The dyestuff corresponding toitem 8 of the 1 -I=N N=N foregoing table corresponds to the formula:

C5H11 (tert.) SOaH l H IFCH3 H N=NN=N $0 0011; s'oiH 0 N--CH; H0 40 3.The acid disazo dyestufi of the formula SOaH NH;

1 S GIG-CH! OsH l WhatIclaimis: 1. Acid disazo dyestuffs of the generalformula CH H SO:H NHR Ofi 2- I SO:- CH: sOaH a E Q 2 N= 0 2-0111 K Y Nno 4. The acid disazo dyestufi of the formula s0/2 \ower alkyl I 5H1:(tert) 50:11 171111 l S0111 aryl N=N-N=N wherein X stands for onesubstituent selected Q I fromthe group consisting of N-CH: HO

Oaryl-R1, O--aralkyl 0H, J A

lower alkyl (MG-CH: O H

SO:aryl

aralkyl FRANZ FRISCH.

53? REFERENCES CITED The following references are of record in the mlkylfile of this patent: aryl STATES PATENTS -so,N Number Name Date lowermy] 2,222,749 Krebser Nov. 26, 1940 mlkyl FOREIGN PATENTS Number CountryDate ycioiiexyl 7 4 ,5 France Oct. 11, .1909

2. THE ACID DISAZO DYESTUF OF THE FORMULA